ES2239374T3 - FURILMETIL CYCLOPROPANOCARBOXYLATE PESTICIDES. - Google Patents

Abstract

Ester compounds represented by the following formula (I) in which R is a methyl, ethyl, n-propyl or aryl group, have excellent effects on the control of harmful pests and are therefore useful as active pesticide ingredients.

Description

Furymethyl Pesticides cyclopropanecarboxylates.

The present invention relates to a compound of ester and a pesticide that contains it as an ingredient active.

The object of the present invention is to provide a compound that has an excellent effect for control harmful pests such as arthropods (including insects, mites, ticks, spiders, etc.) and nematodes. As a result, it has observed that an ester compound represented by the following formula (I):

one

in which R is a methyl group, ethyl, n-propyl or ally,

It has an excellent effect for control pests harmful.

That is, the present invention provides a ester compound represented by formula (I) before represented (hereinafter referred to as "compound of the present invention ") and a pesticide that contains it as an ingredient active.

The compound of the present invention can be produce for example through a process that involves doing react an alcohol compound represented by the following formula (II):

2

in which R is as defined before,

with a carboxylic acid represented by the following formula (III):

3

or a reactive derivative of same.

Among the examples of reactive derivatives of carboxylic acid includes an acid halide compound and a acid anhydride compound.

It is preferable to carry out the reaction of the alcohol compound represented by formula (II) with the acid carboxylic represented by formula (III) in a solvent inert in the presence of a suitable condensing agent, if it is necessary. It is also preferable to carry out the reaction of the alcohol compound represented by formula (II) with the reagent derivative mentioned above in an inert solvent in presence of a base, if necessary. Among the agent examples Condensation includes dicyclohexylcarbodiimide (DCC), and hydrochloride 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (WSC). Among the examples of the base that can be use include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine and diisopropylethylamine. Between Examples of solvent that can be used are included hydrocarbons such as benzene, toluene and hexane; ethers as ether diethyl and tetrahydrofuran and halogenated hydrocarbons as dichloromethane and 1,2-dichloroethane.

The reaction period is comprised Normally between 5 minutes and 72 hours.

The reaction temperature may vary. preferably within the range of -20 ° C and the point of boiling solvent used for the reaction or 100 ° C, more preferably between -5 ° C and the boiling point of the solvent used for the reaction or a temperature of up to 100 ° C. The molar ratio of the alcohol compound represented by the formula (II) to the carboxylic acid represented by the formula (III) or the reactive derivative thereof used can be established optionally, but it is advantageous to establish an equimolar relationship or a relationship similar to the equimolar relationship. The agent of condensation or base can be used in an amount within an interval between an equimolar quantity and an amount in excess, preferably between an equimolar amount and 5 moles, for every 1 mole of the alcohol compound of the formula (II).

Once the reaction is complete, it can be submitted the reaction solution to a conventional treatment as per example extraction with an organic solvent or concentration to give the compound of the present objective invention. If required, it can be purified through a usual procedure as per example chromatography and / or distillation.

The compounds of the present invention have stereoisomers, ie optical isomers (R, S) and isomers geometric (cis / trans and E / Z), and all stereoisomers and mixtures of those who have activity to control harmful pests are included within the present invention.

In the previous production process, the acid carboxylic represented by the formula (III) that is used as starting material can be prepared for example through the method described in Bull. Chem. Soc., Jpn. 4385-4394 (1987).

In the previous production process, the alcohol compounds represented by formula (II) which are used as another starting material include alcohol 5-methyl-2-furfuryl, alcohol 5-ethyl-2-furfuryl, alcohol 5-propyl-2-furfuryl and alcohol 5-aryl-2-furfuryl, which can be prepared according to the usual way.

Among the examples of harmful pests against that the compound of the present invention has an effect of Control insects, mites and ticks are included:

Hemiptera

Delfácidos (bedbugs) such as Laodelphax striatellus (small brown bed bug), Nilaparvata lugens (brown bed bug) and Sogatella furcifera (white backed rice bug); Cicadeloideos (lobsters) like Nephotettix cincticeps (green rice lobster) Neophotettix virescens (green rice lobster) and Recilla dorsalis ; Aphidoids (aphids); aphids such as pentatomids, acanthomatids, urostilids, dinidaeids, chirps and allyds; aleirodids (whiteflies); tíngidos (aphids); psyllids (jumping aphids),

Lepidoptera

Pyralids such as Chilo suppressalis (rice borer), Cnaphalocrocis medinalis (rice leaf bug insect) and Plodia interpunctella (flour moth); Noctids such as Spodoptera litura (tobacco caterpillar), Pseudaletia separata (rice borer), Mamestra brassicae (pumpkin borer); lost like Pieris rapae crucivora (common cabbage butterfly); Tortrícidos as Adoxophyes spp. ; Carposinides; lionetids; limantrids (grass moths); Bankers; Agrotis spp. as Agrotis segetum and Agrotis ipsilon (black caterpillar); Heliotis spp .; Plutella xylostella (diamond back moth); Tinea pellionella (suitcase moth) Tineola bisselliella (tissue moths).

Diptera

Culex spp. such as Culex pipiens pallens (common mosquito) and Culex tritaeniorhynchus; Aedes spp. like Aedes aegypti and Aedes albopictus ; Anopheles spp. as Anopheles sinensis ; Chironomids (dwarf flies); Muscles such as Musca domestica (housefly), Muscina stabulans (fake housefly) and Fannia canicularis (minor housefly); Califorids, Sarcophagi; Antomids such as Delia platura (corn cresa); and Delia antiqua (onion cresa); Tephritids (fruit mosquitoes); Drosophiles; psychedes (moth flies); Simulids (flies); Tabánidos; Stomóxidos; Ceratopogonides (biting dwarf flies);

Coleoptera (beetles)

Diabrotica spp. (corn worms) such as Diabrotica virgifera (western corn worm ) and Diabrotica undecimpunctata howardi (southern corn worm); Scarabéidos like Anomala cuprea and Anomala rufocuprea (bumblebee cuprous); Curculionides such as Sitophilus zeamais (corn weevil) and Lissorhoptrus oryzophilus (rice weevil); Tenebrionids (black beetles) such as Tenebrio molitor (miller beetle) and Tribolium castaneum (brown beetle); Chrysomelids such as Phyllotreta striolata (scrubber beetle) and Aulacophora femoralis (curcubite stripper beetle); Anóbidos; Epilachna spp. as Epilachna vigintioctopunctata (ladybug); lctids (spray beetles); Bostriquids (fake spray beetles); Cerambicids; Paederus fuscipes (clothing beetles);

Dictopters

Blattella germanica (blonde cockroach); Periplaneta fuliginosa (smoked cockroach); Periplaneta americana (American cockroach); Periplaneta brunnea (brown cockroach); Blatta orientalis (black cockroach);

Thysanoptera

Thrips palmi; Thrips hawaiiensis (flower thrips);

Hymenoptera

Formids (ants); vespids (hornets); Betilids; Tentredinids, such as Athalis rosae ruficornis (cabbage fly); etc.

Orthoptera

Grillotálpidos (crickets); acridids (grasshopper);

Siphonaptera

Ctenocephalides canis (canine flea); Ctenocephalides felis (feline flea); Pulex irritans;

Anoplura Pediculus humanus capitis; Pthirus pubis; Isoptera Reticulitermes speratus; Coptotermes formosanus; Tetraniquids

Tetranychus cinnabarinus (spider mites); Tetranychus urticae (two-point spider mite); Tetranychus kanzawai ( Kanzawa spider mite); Panonychus citri ( citrus red mite); Panonychus ulmi (European red mite);

House dust mites

Accharides; Dermatophagoidines; Pyroglyphs; Cheilétides; Macronisides such as Ornithonyssus spp.

Ticks

Ixodids such as Boophylus microplus;

The compound of the present invention used As an active ingredient a pesticide is normally formulated mixing it with a solid vehicle, a liquid vehicle, a vehicle gas or a bait, or is impregnated with a base material of a mosquito mat or a mosquito serpentine for fumigation by electric heating.

When necessary, an agent is added surfactant, an adherent agent, a dispersing agent, a stabilizer and other auxiliaries or additives.

Among the examples of compound formulations of the present invention oily solutions are included, emulsifiable concentrates, wettable powders, formulations fluids, granules, powders, aerosols, chemical fumigants or fuels, such as mucus streamers, mats for mosquitoes for electric heating fumigation and fumigants porous ceramics, volatile formulations applied on a resin or paper, nebulizer formulations, ULV formulations (formulations for ultra low volume application) and baits poisonous

These formulations include the compound of the present invention as an active ingredient in an amount between 0.001% and 95% by weight.

Among the examples of solid vehicles that they can use fine powders or clay granules (e.g., kaolin clay, land of diatoms, synthetic hydrated silicon oxide, bentonite, clays of Fubasami, acid clays), talc, ceramics, other minerals organic (e.g., sericite, quartz, sulfur, active carbon, carbonate calcium, hydrated silicon oxide) and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride and urea).

Among the examples of the liquid vehicle that you can use in the formulation include water, alcohols as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene, aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and gas oil, esters such as ethyl acetate and acetate butyl, nitriles such as acetonitrile and isobutyronitrile, ethers such as diisopropyl ether and dioxane, acidic amides such as N, N-dimethylformamide and N, N-dimethylacetamide, halogenated hydrocarbons such as dichloromethane, trichloroethane and carbon tetrachloride, sulfoxide dimethyl, vegetable oils such as soybean oil and seed oil of cotton.

Among the examples of gas vehicle or propellant that are used in the formulation are included chlorofluorocarbons, butane gas, LPG (liquefied petroleum gas), ether dimethyl and carbon dioxide.

Examples of surfactants include include alkyl sulfates, alkylsulfonates, alkylarylsulfonates, alkyl aryl ethers, ethers polyoxyethylene alkyl aryl, polyethylene glycol ethers, ethers of polyhydric alcohol and alcohol derivatives.

Among the examples of adherent agents, agents dispersion and other auxiliaries or additives include casein, gelatin, polysaccharides such as starch, gum arabic, derivatives of cellulose and alginic acid, derivatives of lignin, bentonite, sugars and synthetic water-soluble polymers, such as vinyl polyol, polyvinylpyrrolidone and polyacrylic acid.

Examples of stabilizers include PAP (acid isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol Y 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, acids fatty and fatty acid esters.

The base material of the mosquito serpentine may consist of a mixture of a raw plant powder such as wood sawdust and Pyrethrum pomace and a binding agent such as Tabu powder ( Machilus thunbergii powder), starch or gluten.

The base material for the mosquito mat for fumigation by electric heating it can consist of a compacted fibreboard plate made of cotton wool or a mixture of Cotton pulp and eraser.

The fuel fumigant base material includes for example an exothermic agent such as nitrate, a nitrite, a guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose and wood sawdust, a pyrolytic stimulating agent as salt of alkali metal, an alkaline earth metal salt, a dichromate and Chromate, a source of oxygen such as potassium nitrate, an assistant of combustion like melanin and wheat starch, a burden of volume as diatomaceous earth and a bonding agent as glue synthetic

The chemical fumigant base material includes for example an exothermic agent such as a sulfide of alkali metal, polysulfide, hydrogensulfide, hydrated salt and oxide calcium, a catalytic agent such as carbonaceous substances, carbide of iron and activated clay, an organic foaming agent such as azodicarbonamide, benzenesulfonylhydrazide, N, N'-dinitrosopentamethylene tetramine, polystyrene and polyurethane and a filler such as synthetic fibers or natural

Among the examples of agent base material volatile thermoplastic resins, filter paper and paper are included Japanese.

The base material of poisonous baits includes a component of bait such as grain powder, vegetable oil, sugar and crystalline cellulose, an antioxidant such as dibutylhydroxytoluene and nordihydroguaarretic acid, a substance to prevent wrong ingestion, such as red pepper powder, a Attractive ingredient like cheese aroma, onion aroma and oil of peanut.

Fluent formulations are prepared normally finely dispersing the compound of the present invention in a ratio of 1 to 75% by weight in water containing 0.5 to 15% by weight dispersing agent, 0.1 to 10% by weight suspension assistant (for example, protective colloid or a thixotropy compound) and 0 to 10% by weight of additives (per example, an antifoam, an agent to prevent rust, a stabilizer, a developer, a penetration assistant, an antifreeze agent, a bactericide, a fungidide).

The compound of the present invention can be disperse in oil, in which the compound of the present invention be substantially insoluble, to form oily suspensions.

Examples of protective colloids include include gelatin, casein, gums, cellulose ethers and polyalcohol Vinyl The thixotropy compound can be bentonite, magnesium aluminum silicate, xanthan gum and polyacid acrylic.

The formulations thus obtained are used according to they are prepared or diluted with water and can be used simultaneously with another insecticide, another acaricide, another nematocide, a bactericide, a herbicide, a regulator of plant growth, a synergy agent, a fertilizer or a floor conditioner without pre-mixing or mixing previous.

Examples of synergy agents include piperonyl butoxide, N- (2-ethylhexyl) bicyclo [2.2.1] hept-5-en-2,3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl- 4-methylbicyclo [2.2.1] oct-5-eno-2,3-dicarboximide and 1,1'-oxybis (2,3,
3,3-tetrachloropropane). Said synergy agent is normally used in an amount comprised between 0.2 and 50 parts by weight per 1 part by weight of the compound of the present invention. The combination of the compound of the present invention and piperonyl butoxide is especially preferable. The weight ratio of the compound of the present invention and piperonyl butoxide is usually 1: 0.2 to 1:50, preferably 1: 0.5 to 1:25, more preferably between 1: 1 and 1:20 .

The insecticides, acaricides and nematocides that used together with the compounds of the present invention include organophosphorus compounds such as fenitrotion [O- (3-methyl-4-nitrophenyl) phosphorothioate of O, O-dimethyl], fenthion [O- [3-methyl-4- (methio) phenyl] phosphorothioate of O, O-dimethyl], diazinon [O-2-isopropyl-6-methylpyrimidin-4-yl O, O-diethyl phosphorothioate], chlorpyrifos [O-3,5,6-trichloro-2-pyridyl O, O-diethyl phosphorothioate], acetate [O, S-dimethyl acetylphosphoramodothioate], metidation [O, O-dimethylphosphorodithioate of S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl], disulfoton [S-2-ethylthioethyl O, O-diethyl phosphorodithioate], DDVP [dimethyl 2,2-dichlorovinyl phosphate], sulprofos [O-4- (methylthio) phenyl S-propyl O-ethyl phosphorodithioate] cyanophos [O, O-dimethyl phosphorothioate O-4-cyanophenyl], dioxabenzophos [2-methoxy-4H-1,3,2-benzodiaxaphosphorin-2-sulfide], dimethoate [S-methylcarbamoylmethyl phosphorodithioate O, O-dimethyl], fentoate [dimethoxyphosphinothiocyl (phenyl) ethyl acetate], malation [O, O-dimethyl phosphorodithioate of 1,2-bis (ethoxycarbonyl) ethyl], trichlorfon [2,2,2-trichloro-1-hydroxyethylphosphonate dimethyl], azinphos-methyl [S - [(4-oxo-1,2,3-benzotriazin-3- (4H) -yl) methyl O, O-dimethyl] phosphorodithioate, monocrotophos [(E) -1-methyl-2- (methylcarbamoyl) vinyl dimethyl phosphate] and ethion [S, S'-methylene bis (O, O, O 'phosphorodithioate, O'-tetraethyl], carbamate compounds such as phenobucarb [methylcarbamate of 2-sec-butylphenyl], benfracarb [N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothium] -N-isopropyl-? -Alaninate of ethyl], propoxur [methylcarbamate of 2-isopropoxyphenyl], carbosulfan [(dibutylaminothium methylcarbamate of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl], carbaryl [1-naphthyl methylcarbamate], methyl [N- (methylcarbamoyloxy) thioacetimidate of S-methyl], etiofencarb [methylcarbamate of 2- (ethylthiomethyl) phenyl], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyl oxime], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], Phenothiocarb [dimethylthiocarbamate of S-4-phenoxybutyl] and methoxadiazone [5-methoxy-3- (2-methoxyphenyl) -1,3,4-oxadiazol-2 (3H) -one], pyrethroid compounds such as etofenprox [ether 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl], fenvalerate [2- (4-chlorophenyl) -3-methylbutyrate from α-cyano-3-phenoxybenzyl], sphevalerate [(S) -2- (4-chlorophenyl) -3-methylbutyrate from (S) - α-cyano-3-phenoxybenzyl], fenpropatrin [2,2,3,3-tetramethylcyclopropanecarboxylate of α-cyano-3-phenoxybenzyl], cypermethrin [3- (2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate from α-cyano-3-phenoxybenzyl], permethrin [3- (2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate of 3-phenoxybenzyl], cyhalotrin [(Z) -3- (2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from α-cyano-2-phenoxybenzyl], deltamethrin [(1R) -cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate from (S) - α-cyano-3-phenoxybenzyl], cycloprotrin [2,2-Dichloro-1- (4-ethoxyphenyl) -cyclopropanecarboxylate from α-cyano-3-phenoxybenzyl], fluvalinate [N- (2-Chloro-?,?,? -Trifluoro-p-tolyl) -D-vanylate from α-cyano-3-phenoxybenzyl], biphentrine [(Z-) 3- (2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 2-methylbiphenyl-3-ylmethyl], ether 2-methyl-2- (4-bromodifluoromethoxyphenyl) propyl 3-phenoxybenzyl, tralometrine [(1R, cis) -3- (1,2,2,2-tetrabromoethyl) -2,2-dimethylcyclopropanecarboxylate from (S) - α-cyano-3-phenoxybenzyl], silafluofen [(4-ethoxyphenyl) [3- (4-fluoro-3-phenoxyphenyl) propyl] dimethylsilane], d-fenotrin [(1R) -crisantemate of 3-phenoxybenzyl], kyphenotrin [(1R) -chisantemate of α-cyano-3-phenoxybenzyl], d-resmethrin [(1R) -crisantemate of 5-benzyl-3-furylmethyl], acrinatrina [(Z) - (1R, cis) -2,2-dimethyl-3- [2- (2,2,2-trifluoro-1-trifluoromethylene oxycarbonyl) vinyl] cyclopropanecarboxylate from (S) - α-cyano-3-phenoxybenzyl], ciflutrin [3- (2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate from α-cyano-4-fluoro-3-phenoxybenzyl], teflutrin [(Z) -3- (2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 2,3,5,6-tetrafluoro-4-methylbenzyl], transflutrin [(1R, trans) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane 2,3,5,6-tetrafluorobenzyl carboxylate], tetramethrin [chrysanthemum of 3,4,5,6-tetrahydroftalimidomethyl], aletrin [chrysanthemum of 3-allyl-2-methyl-4-oxocyclopent-2-enyl], pralethrin [(1R) -crisantemate of (S) -2-methyl-4-oxo-3- (2-propynyl) cyclopent-2-enyl], empentrine [(1R) -cirsantemate of (E) -1-ethynyl-2-methyl-2-pentenyl], imiprotrin [(1R) -crisantemate of 2,5-dioxo-3- (prop-2-inyl) imidazolidin-1-yl-methyl], d-furamethrin [(1R) -crystalline of 5- (prop-2-inyl) furfuryl] and 2,2,3,3-tetramethylcyclopropanecarboxylate 5- (prop-2-inil) furfuryl, thiadiazine derivatives such as buprofezin [2-tert-Butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one], nitroimidazolidine derivatives, nereistoxin derivatives such as cartap [bis (thiocarbamate) of S, S '- (2-dimethylaminotrimethylene)], thiocyclam [N, N-dimethyl-1,2,3-tritian-5-ylamine], and bensultap [di (benzene sulphonate) of S, S'-2-dimethylaminotrimethylene], N-cyanoamidine derivatives as N-cyano-N'-methyl-N '- (6-chloro-3-pyridylmethyl) acetamidine, chlorinated hydrocarbons such as endosulfam [3-oxide 6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methane-2,4,3-benzodioxatiepine], γ-BHC [1,2,3,4,5,6-hexachlorocyclohexane] and dicofol [2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol], benzoylphenylurea compounds such as chlorfluazuron [1- [3,5-Dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-Dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea] and flufenuxuron [1- [4- (2-Chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea], formamidine derivatives such as amitraz [N-methylbis (2,4-xylyliminomethyl) amine] and clordimeform [N '- (4-chloro-2-methylphenyl) -N, N-dimethylmethanamidamide], thiourea derivatives such as diafentiuron [1-tert-butyl-3- (2,6-diisopropyl-4-phenoxyphenyl) thiourea], phenylimidazole derivatives, phenylpyrazole derivatives, bromopropylate [4,4'-dibromobenzylate of isopropyl], tetradifon [4-chlorophenyl-2,4,5-trichlorophenyl sulfone], quinomethionat [S, S- (6-methylquinoxalin-2,3-diyl) dithiocarbonate], propargite [prop-2-inyl sulfite of 2- (4-tert-butylphenoxy) cyclohexyl], fenbutatin oxide [ bis [tris (2-methyl-2-phenylpropyl) tin], hexithiazox [trans-5- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxo-3-thiazolidinecarboxamide], clofentezine [3,6-bis (2-chlorophenyl) -1,2,4,5-tetrazin], pyridaben [2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one], fenpyroximate [(E) - α- (1,3-dimethyl-5-phenoxypyrazol-4-ylmethylene aminoxy) -p-toluate of tert-butyl], tebufenpirad [N- (4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methylpyrazol-5-carboxamide], pyrimidiphen [5-Chloro-N- [2- [4- (2-ethoxyethyl) -2,3-dimethylphenoxy] ethyl] -6-ethylpyrimidin-4-amine], abamectin, milbemectin, ivermectin, azadirachtin [AZAD] and polynactin complex including tetranactin, dinactin and trinactin

When the compound of the present is applied invention as an active ingredient in pesticides for agricultural use, the amount of application is generally between 5 and 500 g per 1000 m2. Emulsifiable concentrates, powders Wettable and flowable formulations are diluted with water to a concentration of 0.1 to 1000 ppm. The granules or powders are not Dilute but are used as prepared.

When the compound of the present invention is applies as an active ingredient of pesticides for domestic use, sanitary or hygienic-sanitary of animals, the emulsifiable concentrates, wettable powders and formulations fluents are diluted with water at a concentration between 0.1 and 10,000 ppm. Oily solutions, aerosols, fumigants, volatile agents, nebulizing agents, ULV formulations, baits poisonous and resins or sheet formulations are used according to They are prepared.

Moreover, the compound of the present The invention can be formulated with one or more sublimation substances. Said formulation may consist of a tablet that can be prepare by solidifying a mixture of the compound of the present invention and a sublimation substance fused by heating or compression of the mixture at a pressure of 3 to 15 kg / cm2. The amount of the compound of the present invention in The tablet is generally 1 to 25% by weight. Between substances sublimation are included 2,4,6-triisopropyl-1,3,5-trioxane, tricycle [5,5,1,0] dean, acetone oxime, cabamate amyl, butyl carbamate, para-butylaldehyde, chloroacetanilides, 4-chloro-3-methylphenol, cyclohexanone oxime, diacetamide, dihydroxyhexane, oxalate dimethyl, dimethylquinone, furfural oxime, p-dichlorobenzene, naphthalene and camphor. Formulation may volatilize the compound of the present invention with the Sublimation substance at room temperature. Therefore it is effective against flying insects such as mosquitoes and flies and insects that infest fabrics such as moths in suitcases, fabric moths and clothing beetles. Since the Sublimation substances have insecticidal activity, you can Expect an additive or synergistic effect.

The amount and concentration of the application may optionally vary according to the type of formulation, the time, place and method of application, as well as the type of Harmful and harmful plague.

Examples

The following will illustrate the present invention in greater detail through production examples, Examples of formulation and biological tests.

Production example one

Chloride (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethyl-cyclopropanecarbonyl (2282 mg) with ice-cold to a mixed alcohol solution 5-methyl-2-furfuryl (1000 mg), 2,6-di-tert-butyl-4-metiphenol (5 mg), pyridine (1057 mg) and toluene (30 ml) and the mixture was maintained at room temperature for 8 hours. The mixture was poured reaction in 5% aqueous citric acid solution with cooling with ice and extracted three times with diethyl ether. He washed successively the ether layer successively combined with solution saturated sodium bicarbonate and a saturated chloride solution sodium and dried over anhydrous magnesium sulfate. After remove the solvent under reduced pressure, the residue was subjected thus obtained by column chromatography on silica gel (eluent; n-hexane / ethyl acetate = 30/1) to give 2495 mg from (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-methyl-2-furfuryl [compound of the present invention (1)]

Yield: 83%

n_ {29}; 1,4681

1 H NMR (internal standard; TMS, in CDCl 3) δ values (ppm):

1.28 (s, 3H), 1.29 (s, 3H), 2.00 (d, 1H), 2.16 (dd, 1H), 2.31 (s, 3H), 5.00 (s, 2H), 5.92 (d, 1H), 6.28 (d, 1H), 6.92 (d, 1 H)

Production example 2

Chloride was added (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethyl-cyclopropanecarbonyl (2070 mg) with ice-cold to a mixed alcohol solution 5-ethyl-2-furfuryl (1000 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (941 mg) and toluene (30 ml) and the mixture was maintained at room temperature for 8 hours. The mixture was poured reaction in a 5% aqueous solution of citric acid with cooling with ice and extracted three times with diethyl ether. He washed successively the ether layer combined with saturated solution of sodium bicarbonate and a saturated solution of sodium chloride, and it dried over anhydrous magnesium sulfate. After removing the solvent under reduced pressure, the residue obtained was subjected to column chromatography on silica gel (eluent; n-hexane / ethyl acetate = 30/1) to give 2270 mg from (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-ethyl-2-furfuryl [compounds of the present invention (2)]

Yield: 82%

n_ {D} 29: 1.4687

1 H NMR (internal standard; TMS, in CDCl 3) δ values (ppm):

1.23 (t, 3H), 1.29 (s, 3H), 1.31 (s, 3H), 2.01 (d, 1H), 2.18 (dd, 1H), 2.66 (q, 2H), 5.01 (s, 2H), 5.95 (d, 1H), 6.30 (d, 1H), 6.93 (d, 1H).

Production example 3

Chloride was added (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethyl-cyclopropanecarbonyl (1303 mg) with ice-cold to a mixed alcohol solution 5-propyl-2-furfuryl (700 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (592 mg) and toluene (30 mg) and the mixture was maintained at room temperature for 8 hours. The reaction mixture following the same procedure as the example of production 1 to give 1350 mg of (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-propyl-2-furfuryl [compound of the invention (3)]

Yield: 74%

n_ {D} 29: 1.4671

1 H NMR (internal standard: TMS, in CDCl 3) δ values (ppm):

0.98 (t, 3H), 1.28 (s, 3H), 1.29 (s, 1H), 1.58-1.78 (m, 2H), 2.01 (d, 1H), 2.18 (dd, 1H), 2.61 (t, 2H), 5.02 (s, 2H), 5.93 (d, 1H), 6.28 (d, 1H), 6.95 (d, 1H).

Production example 4

Chloride was added (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethyl-cyclopropanecarbonyl (28 mg) with ice cooling to a mixed alcohol solution 5-allyl-2-furfuryl (10 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (13 mg) and toluene (5 ml) and the mixture was maintained at room temperature for 8 hours. The reaction mixture following the same procedure as that of production example 1 to give 17 mg of (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoropro-1-enyl) -2,2-dimethylcyclopranocarboxylate from 5-allyl-2-furfuryl [compound of the present invention (4)]

Yield: 65%

n_ {D} 25: 1.4759

1 H-NMR (internal standard; TMS, in CDCl 3) δ values (ppm);

1.29 (s, 3H), 1.30 (s, 3H), 2.01 (d, 1H), 2.15 (dd, 1H), 3.41 (d, 2H), 5.01 (s, 2H), 5.08-5.21 (m, 2H), 5.84-5.97 (m, 2H), 5.98 (d, 1H), 6.31 (d, 1H), 6.91 (d, 1 H).

Production example 5

Can be produced (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethyl cyclopropanecarboxylate 5-methyl-2-furfuryl [the compound of the present invention can be produced (5) using chloride (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarbonyl instead of chloride (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarbonyl in the production example 1.

Production example 6

Can be produced (1R, trans) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-methyl-2-furfuryl [compound of the present invention (6)] using chloride (1R, trans) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropane carbonyl instead of chloride (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarbonyl in the production examples 1.

Production examples 7-9

Can occur (1R, cis) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-ethyl-2-furfuryl [compound of the present invention (7)], (1R, cis) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-propyl-2-furfuryl [compound of the present invention (8)] and (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropane carboxylate 5-allyl-2-furfuryl [compound of the invention (9)] using chloride (1R, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcycle propanecarbonyl instead of chloride (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropane carbonyl in production examples 4-6.

Production examples 10-12

Can occur (1R, trans) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-ethyl-2-furfuryl [the compound of the present invention (10)], (1R, trans) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate from 5-propyl-2-furfuryl [compound of the present invention (11)] and (1R, trans) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcycle propanecarboxylate 5-allyl-2-furfuryl [compound of the present invention (12)] using chloride (1R, trans) -3- (Z-2-Chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarbonyl instead of chloride (1RS, cis) -3- (Z-2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropane-carbonyl in production examples 4-6.

The alcohol compounds represented by the Formula (II) used in the previous production examples is they can prepare according to the following example.

Preparation of alcohol from 5-methyl-2-furfuryl

Sodium borohydride (515 mg) was added to a mixture of 5-methylfurfural (3 g) and methanol (30 ml) with ice-cooling and the mixture was stirred for 1 hour. Be poured the reaction mixture into 5% aqueous acid solution citric with ice-cold and extracted twice with ether diethyl The ether layer combined successively with a saturated sodium bicarbonate solution and a saturated solution of sodium chloride and dried over anhydrous magnesium sulfate. After if the solvent was removed under reduced pressure, the residue was subjected obtained by column chromatography on silica gel to give 2.3 g of alcohol 5-methyl-2-furfuryl.

Yield: 75%

1 H NMR (internal standard; TMS in CDCl 3) δ values (ppm):

1.71 (t, 1H), 2.31 (d, 3H), 4.53 (d, 2H), 5.96 (d, 1H), 6.17 (d, 1H)

Alcohol preparation 5-ethyl-2-furfuryl

Under a nitrogen atmosphere, a n-butyl n-hexane solution lithium (1.69 M, 69.5 ml) to a mixture of furfuryl alcohol (5 g) and tetrahydrofuran (75 ml) at -78 ° C and the mixture was stirred for 1 hour. Ethyl iodide (9.6 g) was added to the mixture, the mixture at room temperature and stirred for 8 hours. Was poured the reaction mixture to a 5% aqueous solution of citric acid with ice-cold and extracted twice with diethyl ether. Be washed the ether layer combined successively with a solution saturated sodium bicarbonate and a saturated chloride solution sodium and dried over anhydrous magnesium sulfate. After remove the solvent under reduced pressure, the residue was subjected obtained by column chromatography on silica gel to give 1.2 g of alcohol 5-ethyl-2-furfuryl.

1 H-NMR (internal standard; TMS, in CDCl 3) δ values (ppm):

1.22 (t, 3H), 1.72 (t, 1H), 2.62 (q, 2H), 4.56 (d, 2H), 5.91 (d, 1H), 6.19 (d, 1H).

Alcohol preparation 5-propyl-2-furfuryl

Under a nitrogen atmosphere, a n-butyl n-hexane solution lithium (1.69 M, 70 ml) to a mixture of furfuryl alcohol (5 g) and tetrahydrofuran (75 ml) at -78 ° C and the mixture was stirred for 1 hour. After adding propyl iodide (10.4 g) to the mixture, it is let the mixture stand at room temperature and stir for 8 hours. The reaction mixture was subsequently treated following the same procedure as in the previous preparation to give 1.2 g of alcohol 5-propyl-2-furfuryl.

1 H-NMR (internal standard; TMS in CDCl 3) δ values (ppm):

0.98 (t, 3H), 1.53-1.72 (m, 2H), 1.82 (width, 1H), 2.58 (t, 2H), 4.52 (width, 2H), 5.40 (d, 1H), 6.15 (d, 1H).

Alcohol preparation 5-allyl-2-fufuryl

Under a nitrogen atmosphere, a n-butyl n-hexane solution lithium (1.69 M, 70 ml) to a mixture of furfuryl alcohol (5 g) and tetrahydrofuran (75 ml) at -78 ° C and the mixture was stirred for 1 hour. After adding allyl iodide (10.3 g) to the mixture, it is let the mixture stand at room temperature and stir for 8 hours. The reaction mixture was subsequently treated following the same procedure as in the previous preparation to give 0.87 g of alcohol 5-allyl-2-furfuryl.

1 H-NMR (internal standard; TMS in CDCl 3) δ values (ppm):

1.72 (width, 1H), 3.40 (d, 2H), 4.52 (d, 2H), 4.92-5.25 (m, 2H), 5.65-5.98 (m, 1H), 5.98 (d, 1H), 6.19 (d, 1H).

The following are examples of formulation. The parts represent parts by weight in these examples.

Formulation example one

Emulsifiable concentrates

Twenty parts of each of the compounds of the present invention (1) to (12) in 65 parts of xylene, mixed with 5 parts of Sorpol 3005X (surfactant distributed by Toho Chemical Co., Ltd) and stirred sufficiently to give emulsifiable concentrates to 20% of each of the compounds.

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Formulation example 2

Wettable powders

Forty parts of each of the compounds of the present invention (1) to (12) first with 5 parts of Sorpol 3005X and then with 32 parts of Carplex # 80 (fine powder of synthetic hydrated silicon oxide distributed by Shionogi & Co., Ltd.) and 23 parts of 300 mesh diatomaceous earth, and Stir with a mixer to give 40% wettable powders to Each of the compounds.

Formulation example 3

Granulated

1.5 parts of each of the compounds of the present invention (1) to (12) with 98.5 parts of AGSORB LVM-MS 24/48 (granulated vehicle of calcined montmorillonite with a particle diameter of 24 to 48 meshes distributed by OIL DRI Corp.) enough to give 1.5% of granules of each of the compounds.

Formulation example 4

Microparticles

A mixture of 10 parts of each of the compounds of the present invention (1) is added to (12), 10 parts of phenylxylethane and 0.5 parts of Sumidur L-75 (toluylene diisocyanate distributed by Sumitomo Bayer Urethane Co. , Ltd.) to 20 parts of 10% aqueous solution of gum arabic, and stirred with a homomixer to give an emulsion with an average particle diameter of 20 µm. The emulsion is then mixed with 2 parts of ethylene glycol and allowed to react on a 60 ° C water bath for 24 hours to give a thick suspension of microcapsules.
the.

A thickening agent is prepared by dispersing 0.2 xanthan gum parts and 1.0 part of Beagum R (silicate magnesium and aluminum distributed by Sansyo Co., Ltd.) in 56.3 parts of water with ion exchange.

42.5 parts of the thick suspension of anterior microcapsules and 57.5 parts of the former thickening agent to give 10% microencapsulated formulations for each of the compounds.

Formulation example 5

Fluent formulations

A mixture of 10 parts of each of the compounds of the invention (1) to (12) and 10 parts of phenylxylethane to 20 parts of a 10% aqueous solution of polyethylene glycol and stir with a homomixer to give a emulsion with an average particle diameter of 3 µm.

A thickening agent is prepared by dispersing 0.2 xanthan gum parts and 1.0 part of Beagum R in 58.8 parts of water with ion exchange.

Forty parts of the emulsion are mixed anterior and 60 parts of the previous thickening agent to give 10% flowable formulations of each of the compounds.

Formulation example 6

Powder

Five parts of each of the compounds of the invention (1) to (12) with 3 parts of Carplex # 80, 0.3 parts of PAP and 91.7 parts of talc 300 mesh and stirred with a mixer to give 5% powders of each of the compounds.

Formulation example 7

Oily solutions

0.1 parts of each of the compounds of the present invention (1) to (12) in 5 parts of dichloromethane and mix with 94.9 parts deodorized kerosene to give 0.1% oily solutions for each of the compounds.

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Formulation example 8

Oil Based Sprays

An aerosol container is filled with the solution obtained by dissolving 1 part of each of the compounds of the present invention (1) to (12) with 5 parts of dichloromethane and 34 parts deodorized kerosene. Next, the container with a valve and 60 parts of propellant (gas liquefied oil) through the valve in the aerosol canister under pressure to give oil-based aerosols for each of the compounds.

Formulation example 9

Water Based Sprays

An aerosol container with 50 parts is filled of water with ion exchange and a mixture of 0.6 parts of each one of the compounds of the present invention (1) to (12), 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier distributed by Atlas Chemical Co.). TO then the vessel is equipped with a valve and 40 are loaded parts of the propellant (liquefied petroleum gas) through the valve in the spray container under pressure to give base sprays aqueous of each of the compounds.

Formulation example 10

Streamers for mosquitoes

A solution prepared by dissolving 0.3 g of each of the compounds of the present invention (1) to (12) in 20 ml of acetone is mixed homogeneously with 99.7 g of a vehicle for a mosquito serpentine (mixture of Tabu powder, Pyrethrm pomace and sawdust in a ratio of 4: 3: 3). After adding 120 ml of water, the mixture is sufficiently kneaded, molded and dried to give mosquito streamers from each of the compounds.
posts.

Formulation example eleven

Mats for mosquitoes for heating fumigation electric

10 ml of solution are prepared by dissolving 0.8 g of each of the compounds (1) to (12) of the present invention and 0.4 g of piperonyl butoxide in acetone. It is impregnated with 0.5 ml of the solution obtained a base material (a plate of fibrils compacted from a mixture of pulp and cotton swab: 2.5 cm x 1.5 cm x 0.3 cm) homogeneously to give mosquito mats for Each of the compounds.

Formulation example 12

Solutions for fumigation by electric heating

Three parts of each of the compounds (1) to (12) in 97 parts of deodorized kerosene. Be load the solution obtained in a polychloride container of vinyl. A porous absorption wick is inserted into the container which is an inorganic powder solidified with a binder and then it was burned, being able to heat the upper portion of the wick with a heater, to give fumigation devices by electric heating using a liquid for each of the compounds.

Formulation example 13

Fumigants

It is impregnated with a solution, prepared dissolving 100 mg of each of the compounds herein invention (1) to (12) in an appropriate amount of acetone, a plate Porous ceramic (4.0 cm x 4.0 cm x 1.2 cm) to give fumigants for Each of the compounds.

Formulation example 14

Volatile agents

A solution prepared by dissolving 100 is applied mug of each of the compounds of the present invention (1) a (12) in an appropriate amount of acetone on a filter paper (2.0 cm x 2.0 cm x 0.3 mm) and acetone is evaporated to give agents volatile for each of the compounds.

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Formulation example fifteen

Acaricidal sheets

It is impregnated with an acetone solution that contains each of the compounds of the present invention (1) a (12) a filter paper so that the concentration of each of the compounds of the present invention be 1 g / 1 m 2 and evaporate acetone to give acaricidal sheets for each of the compounds.

Formulation example 16

Tablets

Each of the compounds of the mixture are mixed present invention (1) to (12) (0.1 g) and p-dichlorobenzene (1.1 g) melted with heating, they are poured into a mold and solidified to give tablets of each of the compounds.

Compounds of the present are tested invention respectively as an ingredient for a pesticide. In the description given below, the compounds used as a reference (racemic compounds) are indicated by the symbols from table 1.

TABLE 1

4

Biological test one

Emulsifiable concentrates of each of the compounds of the present invention were prepared according to formulation example 1. 13 grams of artificial bait for tobacco worm ( Spodoptera litura ) were placed in a polyethylene vessel (diameter: 11 cm) and impregnated with 2 ml of the 500 ppm emulsion prepared by diluting emulsifiable concentrates with water. Ten larvae were placed in the instar 4 of Spodoptera litura in the polyethylene vessel. After 6 days, the mortality of the larvae was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a mortality of 100%.

Biological test 2

A rice plant stem was immersed for one minute in a 500 ppm aqueous emulsion obtained by diluting each of the emulsifiable concentrates of the compounds of the present invention prepared according to formulation example 1. The plant stem was air dried of rice and placed in a polyethylene glass (diameter: 5.5 cm) where filter paper (diameter: 5.5 cm) was impregnated with 1 ml of water. Approximately 30 brown bug larvae ( Nilaparvata lugens ) were placed in the polyethylene cup. After 6 days, the mortality of the larvae was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a mortality of 90% or more.

Biological test 3

5.5 cm diameter filter paper was placed at the bottom of a polyethylene cup (diameter: 5.5 cm). Then 1 ml of a 50 ppm aqueous emulsion obtained by diluting each of the emulsifiable concentrates of the present invention (1) prepared according to formulation example 1 on the filter paper was poured and approximately 30 worm eggs were placed Southern corn ( Diabrotica undecimpunctata howardi ) and a sprouting corn crop as bait in the polyethylene vessel. After 8 days, the mortality of the larvae that had broken the egg and eggs was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had 100% mortality.

Biological test 4

5.5 cm diameter filter paper was placed at the bottom of a polyethylene cup (diameter: 5.5 cm). Next, 0.7 ml of a 500 ppm aqueous emulsion obtained by diluting each of the emulsifiable concentrates prepared according to formulation example 1 was poured into the filter paper and approximately 30 mg of sucrose was uniformly dispersed as bait. Next, ten female house flies ( Musca domestica) little sensitive to pyrethroids were released into the vessel with a lid. After one day, mortality was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a mortality of 100%.

Biological test 5

5.5 cm diameter filter paper was placed at the bottom of a polyethylene cup (diameter: 5.5 cm). Next, 0.7 ml of a 500 ppm aqueous emulsion obtained by diluting each of the emulsifiable concentrates prepared according to formulation example 1 was poured into the filter paper and approximately 30 mg of sucrose was uniformly dispersed as bait. Two male blond cockroaches ( Blattella germanica ) little sensitive to pyrethroids were released in the glass with a lid. After six days, mortality was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a mortality of 100%.

Biological test 6

0.7 ml of aqueous emulsion obtained by diluting the emulsifiable concentrate prepared for each of the compounds of the present invention according to formulation example 1 was added to 100 ml of water with ion exchange (concentration of active ingredient: 3, 5 ppm). Twenty larvae were released in the last insta of common mosquitoes ( Culex pipiens pallens ) in the water. After one day, the mortality of common mosquitoes was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a mortality of 90% or more.

Biological test 7

Ten female common mosquitoes ( Culex pipiens pallens ) were released in a glass chamber (70 cm x 70 cm x 70 cm: 0.34 m 3). 0.7 ml of a 0.1% oil solution prepared for each of the compounds of the present invention was sprayed according to formulation example 7 with a spray gun at 0.8 atmospheric pressure. After 15 minutes, the rate of mosquitoes removed was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had the mosquito removal rate of 90% or more.

Biological tests 8

A mosquito serpentine containing the compound of the present invention was prepared in an amount of 0.3% according to formulation example 10 for the compounds of the present invention. Ten female common mosquitoes ( Culex pipiens pallens ) were released in a glass chamber (70 cm x 70 cm x 70 cm; 0.34 m 3) and 1.0 g of serpentine for 0.3% mosquitoes They had both ends lit in the glass chamber. After 15 minutes, the rate of mosquitoes removed was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had the 100% mosquito removal rate.

Biological test 9

A solution of acetone was applied for each of the compounds of the present invention to 10 female housefly ( Musca domestica ) in the posterior thoracic region (active ingredient: 5 µg / one housefly) and houseflies were released with water and food. After 24 hours, the percentage of dying flies (two replicates) was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had the percentage of dying specimens of 100%.

Biological test 10

After pouring 0.64 ml of a 0.05% (w / v) acetone solution of the compounds of the present invention into an aluminum plate (lower diameter: 7 cm), the acetone was dried in air. Ten females of houseflies ( Musca domestica ) were released in a polyethylene vessel (diameter: 9 cm; depth: 4.5 cm) and the vessel was sealed with a 16 mesh nylon net to prevent direct contact of houseflies With the compound. The glass was placed face down on the aluminum plate at 25 ° C for 120 minutes. Next, the vessel was removed from the aluminum plate and water and food were provided to the houseflies. After 24 hours, the percentage of dying flies (two replicates) was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had the percentage of dying specimens of 100%.

Biological test eleven

After pouring 0.64 ml of a 0.05% (w / v) acetone solution of the compounds of the present invention into an aluminum plate (lower diameter: 7 cm), the acetone was air dried. Ten females of common mosquitoes ( Culex pipiens pallens ) were released in a polyethylene vessel (diameter: 9 cm; depth: 4.5 cm) and the vessel was sealed with a 16 mesh nylon net to avoid direct contact of the mosquitoes with the compound. The glass was placed face down on the aluminum plate at 25 ° C for 120 minutes. Next, the glass was removed from the aluminum plate and water and food were provided to the mosquitoes. After 24 hours, mortality was examined (two replicates). As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a mortality of 100%.

Biological test 12

Each of the compounds of the present invention was applied with acetone at a concentration previously determined to ten larvae in the intermediate instar of clothing moths ( Tineola bisselliella ) in the central part of the back to administer the active ingredient in a dose of 3 \ mug / insect. A percal cloth (2 cm x 2 cm in size) was provided to the clothing moths as food. After 7 days, the mortality and the degree of damage of the calico fabric caused by the moths (two replicates) were examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had a 100% mortality without damage. In contrast, a group of moths treated with acetone that did not contain active ingredient had a 0% mortality and severe damage.

Biological test 13

A percal cloth (2 cm x 2 cm in size) was placed at the bottom of a polyethylene cup (bottom diameter: 10 cm, diameter of the open part: 12.5 cm, height: 9.5 cm, volume: 950 cm3). Ten larvae were placed in the intermediate instar of clothing moths ( Tineola bisselliella ) in the vessel and each of the volatile agents prepared according to formulation example 14 was hung from the lid inside the vessel. After keeping it at 25 ° C for 1 week, the vessel was opened, and the mortality and degree of damage of the calico produced by the moths (two replicates) was examined. As a result, it was observed that the compounds of the present invention (1), (2), (3) and (4) had 100% mortality and no damage.

Biological test 14

A filter paper (3.2 cm x 3.2 cm in size) treated with 36 mg of each of the compounds of the present invention was hung with two calico cloths (25 cm x 25 cm in size) on the part top of a corrugated cardboard box (29 cm x 20 cm x 20 cm in size). After leaving it at 25 ° C and a humidity of 60% for 1 week, a ball was hung to strain the tea that housed 7 to 10 larvae in the intermediate instar of clothing moths ( Tineola bisselliella ) and a piece of calico (2 cm x 2 cm in size) at the top of the box. The box was closed with a lid. After a week, the box was opened and the percentage of dying specimens and the degree of damage of the calico cloth produced by the moths was examined. The same tests were repeated 2 weeks, 3 weeks and 5 weeks after treatment to examine the persistence of the compound of the present invention. Table 2 shows the results. The degree of damage was represented by "-" when there was no damage, "+" when there was slight damage, "++" when there was enough damage and "+++" when there was severe damage.

TABLE 2

5

Biological test fifteen

A certain amount of piperonyl butoxide was added to the compound of the present invention (I) indicated in Table 3. The combination ratio of piperonyl butoxide to the compound of the present invention was 0, 2, 4, 8 and 16 times. The mixture was dissolved in acetone. The acetone solution (0.5 µL) was applied to 10 female housefly ( Musca domestica ) in the dorsal thoracic region. After 24 hours, the number of dead insects (2 repetitions) was observed and mortality was calculated. The results are as shown below.

TABLE 3

Amount treated (\ mug / female) Mortality (%) Compound present invention (1) Butoxide piperonyl 0.5 0 30 0.5 1.0 95 0.5 2.0 100 0.5 4.0 100 0.5 8.0 100 0 8.0 0 Without treating 5

Stability test

Each of the compounds of the compound was dissolved present invention (3.3 mg) in acetone and the solution of resulting acetone on a filter paper (2 cm x 1.5 cm in size) and It was air dried. Separately, a filter paper was treated with powder brass (filter paper in which it had been rubbed in one of its surfaces, 5.5 cm in diameter, approximately 0.03 mg / cm2 of brass powder (Cu / Zn = 76-78 / 22-24) had been rubbed] folded in two turning the surface treated with brass powder inwards. Be kept the previous chemically treated filter paper between the two halves of the folded filter paper, fixed with a clip and placed in a bag with aluminum lamination. It sealed thermally the bag to close it tightly and kept in a vessel at a constant temperature, at 60 ° C for 48 hours. TO the bag was then opened and the color change and the Unpleasant smell of brass dust treated filter paper. As a result, no clear change to a color was observed unpleasant or any color change in any of the compounds (1) to (4).

Sometimes a color change is observed in portions of the fabric that have been ornamented with copper or dyed with dyes that contain copper or an unpleasant smell due to the type of pyrethroid compounds under severe conditions. This essay demonstrates that the compound of the present invention does not have a Unpleasant smell or a color change in severe conditions.

Toxicity test

The compound of the present invention was diluted (1) with corn oil at an appropriate concentration. After subject rats to a 24-hour fast, 0.1 ml of the diluted solution for every 10 g of weight forcedly in the stomach of four male rats 7 weeks old. Food was supplied to the rats and water four hours after application and then He fed them and gave them water regularly by keeping them in a cage. After 7 days, mortality was examined for rats and LD 50 was calculated. Table 4 shows the results.

TABLE 4

Compound LD50 (mg / kg) (one) 300 TO less than 50 B less than 300 more than 100 C less than 100

The compounds of the present invention have a excellent effect to control harmful pests and especially the compound of the present invention in which R is a methyl group It has excellent pesticide activity and low toxicity.

Claims (14)

1. An ester compound represented by the following formula (1): 6 where R is methyl, ethyl, n-propyl or a group ally 2. The ester compound according to claim 1, in which R is a methyl group. 3. The ester compound according to claim 1, in which R is an ethyl group. 4. The ester compound according to claim 1, in which R is an n-propyl group. 5. The ester compound in which the claim 1, in which R is an allyl group. 6. A pesticidal composition comprising a ester compound according to any one of claims 1 to 5 as active ingredient, and a vehicle. 7. A pesticidal composition comprising a ester compound according to any one of claims 1 to 5 as active ingredient, and at least one sublimation substance. 8. The pesticidal composition according to claim 7, wherein the sublimation substance is at least a substance selected from 2,4,6-triisopropyl-1,3,5-trioxane, tricycle [5.5.1.0] dean, acetone oxime, carbamate amyl, butyl carbamate, para-butylaldehyde, chloroacetanilides, 4-chloro-3-methylphenol, cyclohexanone oxime, diacetamide, dihydroxyhexane, oxalate dimethyl, dimethylquinone, furfural oxime, p-dichlorobenzene, naphthalene and camphor. 9. A pesticidal composition comprising a ester compound according to any one of claims 1 to 5 as active ingredient, at least one synergy agent and a vehicle. 10. A pesticidal composition according to claim 9, wherein the synergy agent is at least one selected from piperonyl butoxide, N- (2-ethylhexyl) bicyclo [2.2.1] hept-5-eno-2,3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2.2.1] oct-5-eno-2,3-dicarboximide Y 1,1'-oxybis (2,3,3,3-tetrachloropropane). 11. The pesticidal composition according to claim 9, wherein the synergy agent is butoxide of piperonyl. 12. The pesticidal composition according to claim 11, wherein the weight ratio of the compound of ester according to claim 1 a piperonyl butoxide is found in the range of 1: 1 to 1:20. 13. A method for pest control that comprises the application of an ester compound according to any of claims 1 to 5 to pests or their habitats. 14. Use of an ester compound according to any of claims 1 to 5 for pesticide.